EP0055778B1 - Verfahren zum modifizieren von wollfasern durch entfernen von schuppen - Google Patents

Verfahren zum modifizieren von wollfasern durch entfernen von schuppen Download PDF

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Publication number
EP0055778B1
EP0055778B1 EP81900299A EP81900299A EP0055778B1 EP 0055778 B1 EP0055778 B1 EP 0055778B1 EP 81900299 A EP81900299 A EP 81900299A EP 81900299 A EP81900299 A EP 81900299A EP 0055778 B1 EP0055778 B1 EP 0055778B1
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EP
European Patent Office
Prior art keywords
fiber
scales
fibers
solution
aqueous solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP81900299A
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German (de)
English (en)
French (fr)
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EP0055778A1 (de
EP0055778A4 (de
Inventor
Hiroshi Hojo
Sadao Noguchi
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Individual
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Individual
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Publication of EP0055778A1 publication Critical patent/EP0055778A1/de
Publication of EP0055778A4 publication Critical patent/EP0055778A4/de
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/07—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with halogens; with halogen acids or salts thereof; with oxides or oxyacids of halogens or salts thereof

Definitions

  • the invention relates to a process for refining animal fibers, wherein (a) an oxidation catalyst is absorbed by the hydrophilic connecting portions of the scales and the endocuticle, (b) the fibers are immersed in a solution of a chlorinating agent and an oxidizing agent to pass through the scales Attack oxidation, and (c) treating the fibers with a solution of a reducing agent.
  • animal fiber is intended to extend to those fibers which have a fine structure with scales and are obtained from land mammals such as sheep, goats, llama, alpaca and other animals corresponding to these, while the term“ fur extends to that what is covered with these fibers of the scale structure mentioned above.
  • the invention in contrast to the conventional methods for treating wool, essentially relates to modifying and improving the quality of products made from animal fibers by merely decomposing and detaching the flakes of the animal fibers without damaging the internal cortical cells.
  • the surface of the animal fibers which are to be treated according to the invention has a fine structure which is covered with scales which are flat in shape and arranged in a laminate-like manner as roof tiles and have extremely water-repellent properties.
  • the interior of the scales, which is covered as a whole with a water-repellent film, consists of proteins, the so-called endocuticle, which has a composition which has a large number of polar groups such as carboxyl groups, amino groups and the like and which easily absorbs water .
  • the sections that are open to the gaps between the scales serve as penetration channels for the water, as shown in FIGS. 1 and 3. The water first penetrates into the endocuticle and swells it so that the edges are lifted until the water finally penetrates completely into the cortex inside the wool.
  • the acids penetrate the inside of the fiber without restriction through the moisture penetration channels, so that it becomes practically impossible to determine the oxidation on the Restrict surface of animal fibers.
  • JP-A-5 536 342 (EP-A-0 019 639) discloses a process of the type mentioned at the outset, in which an acid solution is used as the oxidation catalyst, with which the fibers are brought into contact.
  • the procedure described in the introduction is such that in step (a) the oxidation catalyst consists of acids to be applied to the fibers in vapor form or from aqueous solutions or organic solvent dispersions of salts of transition metals, magnesium or aluminum in the form of a chloride, sulfate , Nitrate or acetate in which the fibers are immersed, and that in step (b) the concentration of the solution of the chlorinating agent or the oxidizing agent is so large that the hydrophilic connecting sections are subjected to vigorous oxidation and the scales are completely removed will.
  • the oxidation is limited to the surface areas of the animal fiber, whereby only the scale areas to which the oxidation acts are detached, so that the treatment takes place under conditions in which the cortex inside the fiber is not damaged in any way.
  • acids such as hydrochloric acid, sulfuric acid, formic acid, acetic acid and the like can be used as the source of hydrogen ions, and in particular should not contain any peroxyl group, for the following reason.
  • Such a compound is an oxidizing agent that oxidizes and decomposes the animal fibers, causing the reaction to proceed further inward.
  • acids such as persulfuric acid, peracetic acid and the like should not be used.
  • the animal fiber which has been treated according to process steps (1) or (2) above, in a solution of an alkali metal salt, e.g. B. hypochlorite, chlorite or chlorocyanuric acid or in a solution of an oxidizing agent, e.g. As per sulfuric acid, peracetic acid or potassium permanganate immersed, whereby a strong oxidizing decomposition takes place at the limited endocuticular sections by the oxidizing agent due to the positive catalytic action of the hydrogen ions or the metal bound to the endocuticular sections. This simply removes the scales without damaging the inner cortex in other areas.
  • an alkali metal salt e.g. B. hypochlorite, chlorite or chlorocyanuric acid
  • an oxidizing agent e.g. As per sulfuric acid, peracetic acid or potassium permanganate immersed
  • the residue is then dissolved and removed with the aid of a reducing agent such as sodium pyrosulfite, sodium hyposulfite, sodium sulfite or thioglycolic acid, as a result of which the treating surface becomes smooth.
  • a reducing agent such as sodium pyrosulfite, sodium hyposulfite, sodium sulfite or thioglycolic acid
  • the method according to the invention for modifying products made from animal fibers by detaching the scales is shown step by step in detail using exemplary embodiments.
  • a wool sweater made from Australian merino wool with a diameter of 21.5 microns was placed in a hydrogen chloride vapor stream for about 20 minutes and then in an aqueous solution of sodium dichlorocyanurate with 4% available chlorine at 25 ° Celsius and a bath ratio of 1: 15 immersed for 25 minutes, after which it was washed with a rotary washing machine. 3 minutes after washing, the sweater was treated at 30 ° C for 5 minutes in a bath of 5 g / l sodium pyrosulfite and 10 g / I sodium hydrogen carbonate, after which it was washed with water at 40 ° C for 10 minutes. Microscopic examination revealed that the scales had been removed from the sweater thus treated. The sweater had a wonderful shine and showed a crease resistance of 1.4% even after 3 hours of washing in a washing machine, which is almost perfect.
  • the Australian merino wool upper wool was placed in a 0.015% nickel chloride solution or an aqueous solution of 36 ppm based on the nickel ions; immersed at 28 ° Celsius for 10 to 15 seconds and washed immediately with water.
  • the upper wool was then immersed in a solution of sodium hypochlorite with an available chlorine content of 6% by weight at a bath ratio of 1:15, which was adjusted to pH 6.5 by adding hydrochloric acid and kept at 20 ° Celsius. After the solution was circulated for 2 minutes, the water was removed from the upper wool and washed with water.
  • the upper wool was then immersed in a solution of 5 g / l sodium pyrosulfite and 7 g / l aqueous ammonia (25% solution) at a bath ratio of 1:15 for 3 minutes. After water was removed from the wool, a mechanical procedure was used and the flakes that separated and were detached were washed away.
  • the upper wool was then immersed in a bath of 5 ml / l formalin (35%) with a liquid ratio of 115 at 50 ° C. for 30 minutes, whereupon the water was removed from it, washed with water and dried at the end of the treatment.
  • the wool treated in this way had a wonderful sheen and a smooth, soft feel. Microscopic examination revealed that at least 90% of the scales had been removed. The test result was therefore similar to that which could be obtained according to Example 1.
  • a men's sweater knitted from a double-twisted yarn of this 33 gauge wool with a 12-gauge FF knitting machine had a wrinkle resistance that was able to withstand washing in a washing machine, and an elasticity such as it is unique to wool, has a cashmere-like feel and a cashmere-like bulk, although it didn't feel scratchy when put on.
  • the sweater was covered with an opaque color, e.g. B. crimson, navy blue or black colored, giving it a deep hue that could not be obtained in a conventional manner, and its rub resistance reached class 4 to 5.
  • nickel chloride which is given in (1) of Example 2 of the invention
  • sodium hypochlorite which is given as (2) in Example 2 as the oxidizing agent
  • sodium chlorite sodium chlorocyanurate, potassium chlorocyanurate, chlorinated amines, monopersulfuric acid, persulfuric acid, peracetic acid and hydrogen peroxide.
  • Example 3 In addition to sodium pyrosulfite, which is stated as a reducing agent under (3) in Example 3, it is also possible to use sodium hyposulfite, sodium sulfite or thioglycolic acid.
  • the invention can be used to improve the quality of mixed spun products consisting of an animal fiber and a synthetic fiber, the scales being removed from the animal fiber. It can also be used extensively as a quality improvement process for furs which have a poor quality handle due to the presence of dandruff and where the tips of the hair tend to tangle.
  • the treatment according to the invention can be carried out at a temperature close to normal temperature in a few minutes, the dyes hardly decompose and the appearance which has been imparted to the fiber product, for example by twisting, knitting, sewing and the like, is not lost.
  • the fiber product can thus be modified to a high quality product without adversely affecting the strength of the fiber or the leather parts of the fur.
  • Figure 1 and photo No. 1 show the arrangement of the scales 1, which are arranged on the surface of animal fibers one above the other like roof tiles.
  • Coil-like cells which are referred to as Cortex 5, form their inner layer, the scales 1 being covered with patches 4, which represents a water-repellent film.
  • the surface of the animal fiber therefore has water-repellent properties.
  • the spaces between the scales form a channel 2, which has open hydrophilic sections, as shown in FIG. 3.
  • the hydrophilic section which continues the endocuticular section, which is represented by dotted lines, absorbs water from the channel section 2 when the animal fiber is immersed in water, so that the surface has water-repellent properties.
  • the scales are raised and the fibers can become matted. This phenomenon is well known and is one of the properties and disadvantages of animal fiber which is inherent to it and which does not occur with other fibers.
  • the invention turns this disadvantage into an advantage.
  • chemicals which serve as oxidation catalysts are adsorbed on the hydrophilic channel 2 and the hydrophilic section of the endocuticle 3.
  • the hydrophilic channel 2 and the part of the endocuticle 3 undergo rapid decomposition and dissolution so that the scales 1 collapse and on the inside that is in contact with the inner layer 5 , be replaced.
  • the oxidation is then terminated with a reducing agent, at the same time the remaining parts are removed in a reductive way, so that only the scale areas are detached from the animal fiber, as shown in FIG. 2 and photo no.
  • the inside of the scales has a structure which swells easily and can be easily lifted, the method according to the invention has no influence on the inner layer, but only this swelling part is released in order to detach the scales.
  • the scales 1 of the animal fiber are covered with a water-repellent film, which is referred to as “epicuticle 4, whereby overall a water-repellent property is imparted and they are wetted acum.
  • epicuticle 4 On the back of the scales 1, however, there is a protein layer, referred to as “endocuticulum 3 ”, which has a large number of polar groups and is open to the gap between the scales, as a result of which water can easily pass through.
  • the animal fiber is immersed in an aqueous solution in which, based on the aqueous ion or complex ion, 20 to 50 ppm traces of a transition metal (transition element), such as cobalt, nickel, palladium, platinum, copper, iron, are calculated , Chromium, zinc etc. or aluminum or magnesium, or in an organic solvent in which the above-mentioned aqueous solution is dispersed, the treatment liquid penetrates through those portions which are easy to penetrate in the same manner as the above described acid, so that the metal is adsorbed in a state in which it is bound by coordination to the polar groups of the endocuticle.
  • a transition metal transition element
  • the transition metal is present, the sodium hypochlorite is subsequently decomposed by the catalytic action of the acid, which is a source of hydrogen ions adsorbed on the endocuticle, or the metals specified in the claims lead to the formation of chlorine and oxygen and thus to a rapid local oxidative decomposition as shown in the reaction scheme below: where M represents the transition metal.
  • sodium hypochlorite is used in an amount of 3 to 12% by weight, calculated on the basis of the available chlorine content, based on the weight of the animal fiber to be treated.
  • the scales of the animal fibers are decomposed from the inside to such an extent that they lose their original shape and are thereby detached.

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP81900299A 1980-03-27 1981-01-21 Verfahren zum modifizieren von wollfasern durch entfernen von schuppen Expired EP0055778B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3970280A JPS56140164A (en) 1980-03-27 1980-03-27 Modification of animal fibrous material by scale peeling
JP39702/80 1980-03-27

Publications (3)

Publication Number Publication Date
EP0055778A1 EP0055778A1 (de) 1982-07-14
EP0055778A4 EP0055778A4 (de) 1982-09-03
EP0055778B1 true EP0055778B1 (de) 1985-06-05

Family

ID=12560337

Family Applications (1)

Application Number Title Priority Date Filing Date
EP81900299A Expired EP0055778B1 (de) 1980-03-27 1981-01-21 Verfahren zum modifizieren von wollfasern durch entfernen von schuppen

Country Status (9)

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US (1) US4396388A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
EP (1) EP0055778B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
JP (1) JPS56140164A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
AU (1) AU543073B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA1169606A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE3170786D1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT1137307B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
NZ (1) NZ196636A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
WO (1) WO1981002752A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS58144105A (ja) * 1982-02-12 1983-08-27 Kurabo Ind Ltd スケ−ル除去獣毛繊維の製法
JPS62257458A (ja) * 1986-09-19 1987-11-10 倉敷紡績株式会社 スケ−ル除去獣毛
JPH0482561A (ja) * 1990-07-26 1992-03-16 Niigata High Supinaa Kk 創傷被覆材
JP2567317B2 (ja) * 1991-11-14 1996-12-25 花王株式会社 毛髪化粧料
JP3338975B2 (ja) * 1994-06-07 2002-10-28 博史 北條 ケラチン繊維の改質方法
US7833568B2 (en) * 2005-02-02 2010-11-16 Vartest Labs Inc. Method of determining the cuticle scale height of fibers
JP2006283254A (ja) * 2005-04-04 2006-10-19 Toyobo Co Ltd 脱スケール加工が可能な弾性複合獣毛繊維紡績糸およびそれを用いた防縮加工方法
CN115948806A (zh) * 2023-02-13 2023-04-11 浙江新中和羊毛有限公司 一种羊毛洗毛方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4213437B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1964-05-07 1967-07-31
JPS5536342A (en) * 1978-09-01 1980-03-13 Hiroshi Houjiyou High grade quality improving method of wool fiber substance

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076690A (en) * 1957-05-28 1963-02-05 Daito Boshoku Kabushiki Kaisha Process for the chlorination of wool
US3062610A (en) * 1959-02-10 1962-11-06 Kroy Unshrinkable Wools Ltd Process for shrinkproofing wool
JPS395992B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1961-04-04 1964-04-30
JPS462800B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1967-02-18 1971-01-23
JPS5637368A (en) * 1979-08-30 1981-04-11 Hiroshi Houjiyou High grade modification of animal fiber material

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4213437B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) * 1964-05-07 1967-07-31
JPS5536342A (en) * 1978-09-01 1980-03-13 Hiroshi Houjiyou High grade quality improving method of wool fiber substance

Also Published As

Publication number Publication date
AU6708381A (en) 1981-10-09
DE3170786D1 (en) 1985-07-11
AU543073B2 (en) 1985-03-28
WO1981002752A1 (en) 1981-10-01
EP0055778A1 (de) 1982-07-14
US4396388A (en) 1983-08-02
IT1137307B (it) 1986-09-10
IT8120772A0 (it) 1981-03-27
NZ196636A (en) 1983-05-31
JPS56140164A (en) 1981-11-02
CA1169606A (en) 1984-06-26
JPS6219540B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1987-04-30
EP0055778A4 (de) 1982-09-03

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